Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C409/00—Peroxy compounds
  • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
  • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
  • C07C409/08—Compounds containing six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C407/00—Preparation of peroxy compounds
  • C07C407/003—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C409/00—Peroxy compounds
  • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
  • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
  • C07C409/08—Compounds containing six-membered aromatic rings
  • C07C409/12—Compounds containing six-membered aromatic rings with two alpha,alpha-dialkylmethyl hydroperoxy groups bound to carbon atoms of the same six-membered aromatic ring

Definitions

• the present invention relates to a method for recovering diisopropylbenzene monohydroperoxide of the formula, ##SPC1##
• D-HPO for brevity
• the resulting oxidation product solution is subjected to extraction with an aqueous alkaline solution, whereby the solution is separated into an oily layer containing M-HPO and an aqueous layer containing D-HPO.
• p-diisopropylbenzene is oxidized to afford an oxidation product solution, which is successively followed by cooling to obtain para-D-HPO as crystals.
• the said oily layer containing M-HPO which is considered to be a precursor of D-HPO, can be recycled to the said oxidation.
• M-HPO has a vapor pressure as low as 2.5 ⁇ 10 - 2 mmHg at 84° C, that is, the oxidation product is subjected to distillation in order to clarify the composition of the oxidation product, and then M-HPO is obtained under 2.5 ⁇ 10 - 2 mmHg at 80° to 90° C.
• the present inventors have studied to find a method for the recovery of M-HPO from the oxidation product solution of diisopropylbenzene, which method can be easily carried out in an industrial scale without using disadvantageously severe conditions, and found that M-HPO, which can be reused for the oxidation of diisopropylbenzene without any disadvantage can be recovered by steam-distillation of the oxidation product solution freed from D-HPO according to the conventional method, under a certain condition.
• the present invention provides a method for recovering M-HPO from the oxidation product solution, which comprises separating D-HPO from the oxidation product solution according to the conventional method, and conducting a steam-distillation of the resulting oxidation product solution at pH 6 to 9 and at a solution temperature of 80° to 130° C under a reduced pressure.
• the present invention provides an improvement which comprises adjusting the said oxidation product solution freed from diisopropylbenzene dihydroperoxide to pH 6 to 9, steam-distilling the resulting oxidation product solution at a solution temperature of 80° to 130° C under a reduced pressure, cooling the distillate to be separated into an oily layer containing unoxid
• the oxidation product solution obtained by oxidizing the diisopropylbenzene, for example, using molecular oxygen, is treated to separate D-HPO contained in the solution by the conventional method, such as extraction of D-HPO with an aqueous alkaline solution, and crystallization thereof, which methods are described in British Pat. Nos. 641,250 and 739,907, and the resulting oxidation product solution freed from D-HPO is adjusted to pH 6 to 9, preferably pH about 7, and subjected to the steam-distillation under a reduced pressure.
• the adjusting of the pH can be conducted, preferably by washing the oxidation product solution with water, or by using an acid such as acetic acid and sulfuric acid, or an alkali such as sodium carbonate and sodium hydroxide.
• the reduced pressure is from 20 to 300 mmHg, preferably from 50 to 150 mmHg.
• the solution temperature of the steam-distillation is from 80° to 130° C, preferably from 100° to 110° C.
• the amount of steam to be introduced varies depending upon the distillation temperature, degree of reduced pressure, composition of the oxidation product solution to be steam-distilled and type of a reactor (distillator), but it is usually within a range from about 3 to about 10 times by weight the oxidation product solution freed from D-HPO.
• M-HPO can be distilled out together with steam, and the distillate is cooled through a condenser to separate into an oily layer containing M-HPO and unoxidized diisopropylbenzene, and an aqueous layer.
• the oily layer can be recycled to the oxidation reaction of diisopropylbenzene to obtain D-HPO without any disadvantages.
• M-HPO can be distilled out by steam-distillation of the oxidation product solution containing D-HPO, it is favorable to separate D-HPO prior to the steam-distillation because a thermal decomposition of D-HPO occurs under the conditions mentioned above.
• the oxidation product solution to be subjected to the steam-distillation is favorably neutralized in advance, for example, by washing with water.
• the steam-distillation at below 80° C leads to decrease of a distillation amount of M-HPO, resulting in unfavorable distillation efficiency.
• the steam-distillation at higher than 130° C leads to thermal decomposition of M-HPO to decrease the retention percent thereof, and moreover it is dangerous because the possibility of sudden thermal-decomposition is increased.
• the temperature of the distillate can be lowered with increasing the degree of reduced pressure, but it becomes difficult more and more to condense the distillate by cooling. Therefore, in carrying out the present steam-distillation in an industrial scale, the temperature of the distillate will be determined depending upon the degree of reduced pressure in consideration of several factors concerning a distillation apparatus.
• the distillate can easily be separated into the oily layer containing M-HPO and unoxidized diisopropylbenzene, and the aqueous layer after the condensation by cooling.
• the solubility of M-HPO in the aqueous layer is so negligible that substantially no M-HPO is lost into the aqueous layer.
• Example is only illustrative, but not limitative for the scope of the present invention.
• parts are by weight unless otherwise specified.
• the aqueous layer was separated to obtain 85 parts of an oily layer.
• the oily layer contained 45 parts of the diisopropylbenzene and 40 parts of M-HPO.
• the distillation residue was 15 parts, and contained 4 parts of M-HPO and 11 parts of total byproducts having carbinol group. From the results, the recovery percentage of M-HPO was calculated as 88 % and the retention percentage of M-HPO 98 %.
• the resulting oily layer containing diisopropylbenzene and M-HPO was recycled to the oxidation reaction system, and the oxidation reaction could be carried out efficiently without any disadvantage.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Publications (1)

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Family Applications (1)

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Citations (8)

• 1973
  • 1973-05-02 JP JP4940773A patent/JPS5653546B2/ja not_active Expired
• 1974
  • 1974-04-29 US US05/465,137 patent/US3993696A/en not_active Expired - Lifetime
  • 1974-04-30 DE DE2421039A patent/DE2421039C2/de not_active Expired
  • 1974-04-30 FR FR7415002A patent/FR2228054B1/fr not_active Expired
  • 1974-04-30 IT IT50723/74A patent/IT1011333B/it active
  • 1974-05-01 CA CA198,666A patent/CA1022493A/en not_active Expired
  • 1974-05-01 GB GB1914774A patent/GB1469950A/en not_active Expired

Patent Citations (8)

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